Double dative bond between divalent carbon(0) and uranium

Wei Su,Lili Zhao,Shuao Wang,Congqing Zhu,Xiong Sun,Gernot Frenking,Sudip Pan

doi:10.1038/s41467-018-07377-6

Abstract

Dative bonds between p- and d-block atoms are common but species containing a double dative bond, which donate two-electron pairs to the same acceptor, are far less common. The synthesis of complexes between UCl4 and carbodiphosphoranes (CDP), which formally possess double dative bonds Cl4U⇇CDP, is reported in this paper. Single-crystal X-ray diffraction shows that the uranium−carbon distances are in the range of bond lengths for uranium−carbon double bonds. A bonding analysis suggests that the molecules are uranium−carbone complexes featuring divalent carbon(0) ligands rather than uranium−carbene species. The complexes represent rare examples with a double dative bond in f-block chemistry. Our study not only introduces the concept of double dative bonds between carbones and f-block elements but also opens an avenue for the construction of other complexes with double dative bonds, thus providing new opportunities for the applications of f-block compounds.

Highlights

Dative bonds between p- and d-block atoms are common but species containing a double dative bond, which donate two-electron pairs to the same acceptor, are far less common
We report a set of complexes that possess a double dative bond between carbon and uranium
The results of this study could be useful for the design of other compounds containing f-block atoms that exhibit double dative bonds between the metal and carbone ligands, and could provide new opportunities for the applications of f-block elements in catalysis or in the activation of small molecules

Summary

Introduction

Dative bonds between p- and d-block atoms are common but species containing a double dative bond, which donate two-electron pairs to the same acceptor, are far less common. CR2, which contain one lone electron pair, can coordinate to numerous main group atoms and d-block or even f-block elements forming stable species via a single dative bond. The first divalent carbon(0) species[9], carbodiphosphorane (CDP), was reported already in 1961, the actual bonding situation was not fully understood until a theoretical study appeared in 2006 by Frenking and coworkers[27,28,29] They showed that CDP can be considered as two phosphine ligands coordinated to a carbon atom in the excited 1D state with two lone electron pairs, which remain available for both σ- and π-donation simultaneously[13]. The results of this study could be useful for the design of other compounds containing f-block atoms that exhibit double dative bonds between the metal and carbone ligands, and could provide new opportunities for the applications of f-block elements in catalysis or in the activation of small molecules

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Results

Conclusion